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Article
Solvent-Induced Shifts in Electronic Spectra of Uracil
Journal of Physical Chemistry A
  • Albert DeFusco, Iowa State University
  • Joseph Ivanic, National Cancer Institute at Frederick
  • Michael Schmidt, Iowa State University
  • Mark S. Gordon, Iowa State University
Document Type
Article
Disciplines
Publication Version
Published Version
Publication Date
4-1-2011
DOI
10.1021/jp112230f
Abstract

Highly accurate excitation spectra are predicted for the low-lying n−π* and π−π* states of uracil for both the gas phase and in water employing the complete active space self-consistent field (CASSCF) and multiconfigurational quasidegenerate perturbation theory (MCQDPT) methods. Implementation of the effective fragment potential (EFP) solvent method with CASSCF and MCQDPT enables the prediction of highly accurate solvated spectra, along with a direct interpretation of solvent shifts in terms of intermolecular interactions between solvent and solute. Solvent shifts of the n−π* and π−π* excited states arise mainly from a change in the electrostatic interaction between solvent and solute upon photoexcitation. Polarization (induction) interactions contribute about 0.1 eV to the solvent-shifted excitation. The blue shift of the n−π* state is found to be 0.43 eV and the red shift of the π−π* state is found to be −0.26 eV. Furthermore, the spectra show that in solution the π−π* state is 0.4 eV lower in energy than the n−π* state.

Comments

This article is from Journal of Physical Chemistry A 115 (2011): 4574, doi:10.1021/jp112230f.

Rights
Works produced by employees of the U.S. Government as part of their official duties are not copyrighted within the U.S. The content of this document is not copyrighted.
Copyright Owner
Language
en
File Format
application/pdf
Citation Information
Albert DeFusco, Joseph Ivanic, Michael Schmidt and Mark S. Gordon. "Solvent-Induced Shifts in Electronic Spectra of Uracil" Journal of Physical Chemistry A Vol. 115 Iss. 18 (2011) p. 4574 - 4582
Available at: http://works.bepress.com/mark_gordon/445/